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Main Title: A Pseudotetrahedral Terminal Oxoiron(IV) Complex: Mechanistic Promiscuity in C−H Bond Oxidation Reactions
Author(s): Warm, Katrin
Paskin, Alice
Kuhlmann, Uwe
Bill, Eckhard
Swart, Marcel
Haumann, Michael
Dau, Holger
Hildebrandt, Peter
Ray, Kallol
Type: Article
Abstract: S=2 oxoiron(IV) species act as reactive intermediates in the catalytic cycle of nonheme iron oxygenases. The few available synthetic S=2 FeIV=O complexes known to date are often limited to trigonal bipyramidal and very rarely to octahedral geometries. Herein we describe the generation and characterization of an S=2 pseudotetrahedral FeIV=O complex 2 supported by the sterically demanding 1,4,7‐tri‐tert‐butyl‐1,4,7‐triazacyclononane ligand. Complex 2 is a very potent oxidant in hydrogen atom abstraction (HAA) reactions with large non‐classical deuterium kinetic isotope effects, suggesting hydrogen tunneling contributions. For sterically encumbered substrates, direct HAA is impeded and an alternative oxidative asynchronous proton‐coupled electron transfer mechanism prevails, which is unique within the nonheme oxoiron community. The high reactivity and the similar spectroscopic parameters make 2 one of the best electronic and functional models for a biological oxoiron(IV) intermediate of taurine dioxygenase (TauD‐J).
Subject(s): bioinorganic chemistry
enzyme models
high-valent iron
hydrogen atom abstraction
electron transfer
Issue Date: 15-Feb-2021
Date Available: 24-Jun-2021
Language Code: en
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat"
Journal Title: Angewandte Chemie
Publisher: Wiley
Volume: 60
Issue: 12
Publisher DOI: 10.1002/anie.202015896
Page Start: 6752
Page End: 6756
EISSN: 1521-3773
ISSN: 1433-7851
TU Affiliation(s): Fak. 2 Mathematik und Naturwissenschaften » Inst. Chemie » FG Physikalische Chemie / Biophysikalische Chemie
Appears in Collections:Technische Universität Berlin » Publications

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